JP4807603B2 - Thermosetting resin composition and cured product thereof - Google Patents

Description

  The present invention relates to a liquid thermosetting resin composition containing an imide resin that can be applied or cast. Specifically, when this composition is coated and cured, the heat resistance, flame retardancy, and mechanical properties, which are the original properties of polyimide resin, are further improved, and thermosetting properties are also excellent in dimensional stability. The present invention relates to a resin composition.

  In the heat-resistant coating materials field, electrical insulation materials such as interlayer insulation materials for printed wiring boards and semiconductor insulation materials, build-up materials, prepreg resins, heat-resistant adhesives, etc., the toughness, heat resistance, There has been a demand for a resin composition capable of obtaining a cured product excellent in halogen-free flame retardancy. In particular, there is a strong demand for downsizing such as ultra-thin flexible film substrates and rigid substrates in the field of electronic equipment industries such as computers. In order to respond to this demand, mechanical strength in the protective layer, adhesive layer and insulating layer of the substrate (Toughness), heat resistance, dimensional stability, improvement in flame retardance without halogen, and improvement in thermal decomposition resistance at high temperatures are essential.

  The polyimide resin has excellent heat resistance and mechanical strength, and is preferably used in the electric and electronics industry. As a polyimide resin excellent in heat resistance, mechanical strength and dimensional stability, for example, pyromellitic anhydride and 4,4′-bis (4-aminobenzamide) -3,3′-dihydroxybiphenyl are reacted to form a polyamide. A polyamide obtained by dehydrating and ring-opening this polyamic acid after obtaining an acid is disclosed (for example, see Patent Document 1). However, the polyimide resin disclosed in Patent Document 1 does not have sufficient solvent solubility. For this reason, there is a problem that the applications that can be used are limited.

  Therefore, in recent years, solvent-soluble polyimide resins that are excellent in solvent solubility have been studied actively. For example, a tetracarboxylic acid anhydride and an oxyhydroxide having a structure in which an ester bond is connected to both ends of an alkylene as an acid anhydride as a polyimide resin having excellent solvent solubility and dissolution stability and a flexible cured film. An imide resin having a diamine compound having an alkylene structure as a main component is disclosed (for example, see Patent Document 2). However, since the imide resin described in Patent Document 2 contains an ester bond or an aliphatic ether structure, there is a problem that sufficient heat resistance, dimensional stability, flame retardancy, and heat decomposition resistance at high temperatures cannot be obtained. Have.

  Moreover, the polyimide resin which improved the solvent solubility using aliphatic and / or alicyclic components, such as sebacic acid and cyclohexane dimethanol, as a structural component is also disclosed (for example, refer patent document 3). However, since the polyimide resin described in Patent Document 3 contains an aliphatic structure or an alicyclic structure, the polyimide resin also requires solvent solubility, so sufficient heat resistance, dimensional stability, flame retardancy, high temperature The thermal decomposition resistance at is not obtained.

  Furthermore, a polyimide resin having a carboxyl group, a linear hydrocarbon structure, a urethane bond, and an isocyanurate structure is disclosed as a general-purpose organic solvent-soluble polyimide resin (see, for example, Patent Document 4). Although the polyimide resin disclosed in Patent Document 4 is soluble in solvents other than N-methylpyrrolidone, the polyimide resin alone has poor film-forming properties, and the combined use of an epoxy resin is indispensable. Although a cured coating film obtained by using an epoxy resin in combination has heat resistance, this polyimide resin also has insufficient mechanical properties such as dimensional stability and toughness, and thermal decomposition resistance at high temperatures.

  As described above, in recent years, a polyimide resin excellent in dimensional stability has not been obtained due to much efforts to improve solvent solubility.

JP-A-7-179605 JP 2006-22302 A JP 2007-138000 A JP 2003-292575 A

  The present invention provides a thermosetting resin composition having excellent dimensional stability in addition to heat resistance and mechanical properties, which are inherent characteristics of a polyimide resin, and a cured product obtained by curing the composition when cured. Is to provide.

  As a result of intensive studies, the present inventors have found that a cured coating film in which a resin composition containing an imide resin and a specific boron compound is excellent in flame retardancy, heat resistance and mechanical properties, thermal decomposition resistance at high temperatures, and dimensional stability. What is obtained is a resin composition that is excellent in storage stability and solvent solubility while maintaining the above performance by using a polyimide having excellent solvent solubility described in Patent Documents 2 to 4 among the imide resins. As a result, the present invention has been completed.

  That is, this invention contains the polyimide resin (A) and the boron compound (B) of the following general formula (b3), and the polyimide resin (A) is represented by the following general formula (a1). The present invention provides a thermosetting resin composition, which is a polyimide resin having

（式中Ｒ_３はそれぞれ独立して水素原子、炭素原子数１〜４のアルキル基または炭素原子数１〜４のアルコキシ基を表す。Ｚは含窒素複素環化合物を表す。）

(In the formula, each R ₃ independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Z represents a nitrogen-containing heterocyclic compound.)

  Moreover, this invention provides the hardened | cured material characterized by hardening the said thermosetting resin composition.

  When the thermosetting resin composition of the present invention is formed into a coating film, the coating film is excellent in flame retardancy, toughness, heat resistance, thermal decomposition resistance at high temperatures, and dimensional stability, and is a coating agent and wiring interlayer insulation. Useful for films, adhesives, etc.

It is an infrared absorption spectrum of the polyimide resin obtained in Synthesis Example 1. 2 is a nuclear magnetic resonance absorption spectrum of the polyimide resin obtained in Synthesis Example 1. It is an infrared absorption spectrum of the polyimide resin obtained in Synthesis Example 2. 3 is a nuclear magnetic resonance absorption spectrum of the polyimide resin obtained in Synthesis Example 2.

  The polyimide resin (A) used in the present invention has a cyclic 5-membered imide bond. As such a polyimide resin, for example, a polyimide resin that can be dissolved and dispersed in a solvent can be used. The polyimide resin (A) can be used, for example, as long as it is an imide resin that liquefies when heated at 120 ° C., but is preferably a polyimide resin that is liquid at room temperature.

  The polyimide resin that can be dissolved and dispersed in a solvent with the polyimide resin having a cyclic 5-membered imide bond is, for example, a cyclic imide obtained by further dehydrating a polyamic acid obtained by reacting an acid anhydride-containing compound with a polyamine compound. It can be produced by an amic acid method for forming a bond or an isocyanate method for reacting an acid anhydride-containing compound with a polyisocyanate compound to form a cyclic imide bond by decarboxylation.

  As a method for producing the polyimide resin (A) used in the present invention, the amic acid method needs to use a polar solvent in order to maintain the solubility and stability of the amic acid that is an intermediate formed product. . Therefore, the isocyanate method is preferable. The isocyanate method also has an advantage that a polyimide resin having good compatibility with the boron compound (B) described later can be easily obtained.

  As described above, the polyimide resin (A) used in the present invention is preferably a polyimide resin dissolved or dispersed in a solvent because the mixing workability of each component and the stability of the composition are improved. As such a polyimide resin, for example, a polyimide resin having a structure of the following general formula (a1) can be preferably exemplified.

  When the polyimide resin (A) used in the present invention is a polyimide resin having the structure represented by the general formula (a1), the content of the structure represented by the general formula (a1) is the solid content of the polyimide resin. From 1 to 50% by mass based on mass, it becomes a polyimide resin excellent in solvent solubility, and a cured product excellent in mechanical properties such as heat resistance, tensile strength and elongation, and dimensional stability can be obtained. Preferably, 5-50 mass% is more preferable. Further, since the crystallinity in the thermosetting resin composition of the present invention is reduced, and a cured product having excellent mechanical properties such as heat resistance and elongation at break and dimensional stability is obtained, 10 to 45% by mass is obtained. More preferably, 10-40 mass% is still more preferable.

Examples of the structure represented by the general formula (a1) include a polyimide resin having a divalent structural unit represented by the general formula (a1-2).

（但しＲ_０は、２価のジアミンまたは、ジイソシアネートのアミン基、イソシアネート基を除いた残基構造であり、ａ０は繰り返しを示し、＊は結合点を示す。ａ０は１〜１０００である。）

(However, R ₀ is a divalent diamine or a residue structure excluding an amine group and an isocyanate group of diisocyanate, a0 indicates repetition, * indicates a bonding point, and a0 is 1-1000.)

Among the polyimide resins having the structure represented by the general formula (a1-2), the polyimide resin having one or more structures represented by the general formulas (a1-3) to (a1-8) has a tensile strength. A polyimide having a structure represented by the general formula (a1-7) or (a1-8) is preferable because a cured product having excellent mechanical properties such as elongation and elongation can be obtained and it is easy to become a polyimide resin that can be dissolved in a solvent. It is more preferable that the resin can further reduce the linear expansion coefficient.

In the structures represented by the general formulas (a1-3) to (a1-8), * represents a bonding point, and R ₄ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 9 carbon atoms. a1, a2, a3, a4, a5, and a6 are the number of repeating structural units in parentheses and are 1 to 1000, respectively.

  When the polyimide resin (A) used in the present invention is a polyimide resin having a structure represented by the general formula (a1-2), the content of the structure represented by the general formula (a1-2) 1 to 98% by mass based on the solid content mass of the resin becomes a polyimide resin excellent in solvent solubility, and a cured product excellent in mechanical properties such as heat resistance, tensile strength and elongation, and dimensional stability can be obtained. To 10 to 95% by mass is more preferable. Moreover, since the crystallinity in the thermosetting resin composition of this invention falls and it becomes a thermosetting resin composition excellent in storage stability, 2-90 mass% is more preferable, and 5-80 mass% is still more. preferable.

  When the polyimide resin (A) used in the present invention is a polyimide resin having one or more structures represented by the general formulas (a1-3) to (a1-8), the general formulas (a1-3) to (a1-8) ), The content of the structure represented by 1 to 98% by mass based on the solid content mass of the polyimide resin is a polyimide resin excellent in solvent solubility, and is a machine such as heat resistance, tensile strength and elongation. This is preferable because a cured product having excellent physical properties and dimensional stability can be obtained. Moreover, since the crystallinity in the thermosetting resin composition of this invention falls and it becomes a thermosetting resin composition excellent in storage stability, 2-90 mass% is more preferable, and 5-80 mass% is still more. preferable.

  As the polyimide resin (A) used in the present invention, a polyimide resin having a divalent structural unit represented by the following general formula (a2) is excellent in solvent solubility and compatibility, as well as toughness and heat resistance. It is preferable because a thermosetting resin composition capable of obtaining a cured coating film is obtained.

  Examples of the structure represented by the general formula (a2) include a polyimide resin having a structure represented by the general formula (a2-2).

（Ｒ_０は、２価のジアミンまたは、ジイソシアネートからアミン基、イソシアネート基を除いた残基であり、ａ０は繰り返しを示し、＊は結合点を示す。ａ０は１〜１０００である。）

(R ₀ is a divalent diamine or a residue obtained by removing an amine group or an isocyanate group from diisocyanate, a0 indicates a repetition, * indicates a bonding point, and a0 is 1-1000.)

  Among the polyimide resins having the structure represented by the general formula (a2-1), the polyimide resin having at least one of the structures represented by the general formulas (a2-3) to (a2-8) has a tensile strength or A polyimide resin having a structure represented by the general formula (a2-7) or (a2-8) is preferable because a cured product having excellent mechanical properties such as elongation can be obtained and is easily dissolved in a solvent. Is more preferable because a cured product having a smaller linear expansion coefficient (excellent in dimensional stability) can be obtained.

Said * are structures in which represented by the general formulas (a2-3) (a 2 -8) represents a point of attachment, each _{R 4} is independently a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms. a7, a8, a9, a10, a11, and a12 are the number of repeating structural units in parentheses and are 1 to 1000, respectively. ]

  When the polyimide resin (A) used in the present invention is a polyimide resin having a structure represented by the general formula (a2), the content of the structure represented by the general formula (a2) is the solid content of the polyimide resin. 1 to 98% by mass based on mass is preferable because a cured resin having excellent solvent solubility and mechanical properties such as heat resistance, tensile strength and elongation, and dimensional stability is obtained. -95 mass% is more preferable. Moreover, since the crystallinity in the thermosetting resin composition of this invention falls and it becomes a thermosetting resin composition excellent in storage stability, 2-90 mass% is more preferable, and 5-80 mass% is still more. preferable.

  When the polyimide resin (A) used in the present invention is a polyimide resin having one or more structures represented by general formulas (a2-3) to (a2-8), from general formulas (a2-3) to (a2-8) ), The content of the structure represented by 1 to 98% by mass based on the solid content mass of the polyimide resin is a polyimide resin excellent in solvent solubility, and is a machine such as heat resistance, tensile strength and elongation. This is preferable because a cured product having excellent physical properties and dimensional stability can be obtained. Moreover, since the crystallinity in the thermosetting resin composition of this invention falls and it becomes a thermosetting resin composition excellent in storage stability, 2-90 mass% is more preferable, and 5-80 mass% is still more. preferable.

  Among the polyimide resins (A), the structure represented by the general formula (a2-7) or the general formula (a2-8) is 0.02 to 2 based on the solid content mass of the polyimide resin (A). The polyimide resin contained at a concentration of 0.0 mmol / g is preferable because it becomes a polyimide resin excellent in solvent solubility, and a cured product excellent in mechanical properties such as heat resistance, tensile strength and elongation, and dimensional stability is obtained.

In the case where the polyimide resin (A) has a structure represented by general formula (a1-7), general formula (a1-8), general formula (a2-7), or general formula (a2-8), A polyimide resin in which R ₄ is a methyl group is preferred because a cured product having more excellent heat resistance, mechanical properties such as tensile strength and elongation, and dimensional stability can be obtained.

  Among the polyimide resins (A), a polyimide resin having a structure of the general formula (a1-7) or the general formula (a1-8) and the general formula (a2-7) or the general formula (a2-8) However, it is preferable because a cured product having excellent mechanical properties such as heat resistance, tensile strength and elongation, and dimensional stability can be obtained.

  The polyimide resin (A) preferably has solvent solubility, but when it is dissolved in gamma-butyrolactone so as to be 10% by mass at 25 ° C., a structure that is soluble in gamma-butyrolactone is a cured composition. It is preferable in terms of excellent compatibility and stability over time.

  Moreover, it is preferable at the surface which can obtain the composition excellent in toughness, such as breaking strength, by having the structure represented by the following (a3) type among polyimide resins (A).

  As a polyimide resin which has a structure represented by the said general formula (a3), the polyimide resin which has the following structure can be illustrated, for example.

(R ₀ is a divalent diamine or a residue obtained by removing an isocyanate group from a diisocyanate, a 0 indicates a repetition, * indicates a bonding point, and a 0 is 1-1000.)

  Among the polyimide resins having the structure represented by the formula (a3), the polyimide resin having the following structure is excellent in the stability of the polyimide resin (A), and has mechanical properties such as heat resistance, tensile strength, and elongation. And a cured product having excellent dimensional stability is preferable.

In the structures represented by the general formulas (a3-2) to (a3-4), * represents a bonding point, and R ₄ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 9 carbon atoms. a7, a8, and a9 are 1 to 1000 as the number of repeating structural units in parentheses. )

  The polyimide resin (A) used in the present invention is preferably one that dissolves in an organic solvent. As the organic solvent to be used, for example, a conventionally used polar solvent organic solvent having a large dissolving power such as N-methylpyrrolidone, dimethylacetamide, and methylformamide can be used. Imide resins that are soluble only in solvents and the like have problems such as whitening due to hygroscopicity, and storage stability is insufficient. For this reason, the problem that the coating film (film) obtained using this resin cannot obtain the tough coating film and excellent electrical properties of the original imide resin arises. Therefore, an imide resin that is soluble in an organic solvent having a relatively weak solubility such as gamma butyrolactone (γ-butyrolactone) is more preferable.

  In addition, as the polyimide resin (A) used in the present invention, a polyimide resin that dissolves at around room temperature, for example, 10 to 30 ° C. is preferable, but an imide resin having crystallinity that dissolves at warming, for example, 100 to 150 ° C. It is possible to use. Especially, since the workability | operativity which forms a coating film becomes favorable, the imide resin which is soluble at 10-120 degreeC is more preferable.

  In the present invention, whether or not the polyimide resin (A) used in the present invention is dissolved in an organic solvent is determined by adding the polyimide resin concentration of the present invention to 10% by mass in an organic solvent and adding 7% at 25 ° C. After standing for days and hours, the appearance can be visually observed.

  The polyimide resin (A) used in the present invention is preferable because the polyimide resin dissolved in gamma butyrolactone is a polyimide resin having excellent storage stability, and when dissolved in gamma butyrolactone so that it becomes 10% by mass at 25 ° C. A polyimide resin that is soluble in water is preferred. In order to obtain a polyimide resin that dissolves in gamma butyrolactone, it can be obtained, for example, by a method for producing a polyimide resin described later.

  The polyimide resin (A) used in the present invention may be a polyimide resin having a linear structure or a polyimide resin having a branched structure. Further, the copolymer component may have a polyester-modified polyesterimide or urethane-modified polyurethaneimide structure.

  Examples of the terminal structure of the polyimide resin (A) used in the present invention include structures such as carboxylic acid, carboxylic acid anhydride, isocyanate group, and amine group. As the terminal structure, the structure of the carboxylic acid or its anhydride is preferable because the stability of the polyimide resin itself of the present invention and the stability after blending with an organic solvent or another resin are good. When the terminal structure is a carboxylic acid or its anhydride structure, the acid value is a polyimide resin with a solid content acid value of 1 to 50 that is easy to handle, and a film or molded product having excellent mechanical strength and dimensional stability can be obtained. To preferred.

  The molecular weight of the polyimide resin (A) used in the present invention is preferably from 1,000 to 200,000, and more preferably from 2,000 to 100,000, since a polyimide resin (A) that is easy to handle and a film or a molded product having excellent mechanical strength and dimensional stability can be obtained. The molecular weight can be measured by GPC or quantitative determination of the terminal functional group.

The polyimide resin (A) that can be used in the present invention can be produced, for example, by the following method.
Production method 1: A method of directly imidizing a polyisocyanate compound and a compound having an acid anhydride group (isocyanate method).
Production method 2: A method in which a compound having an acid anhydride group and a diamine compound are reacted to synthesize an amic acid, followed by a dehydration reaction of the amic acid to cause imide ring closure.

  In order to produce a polyimide resin used in the present invention, it is possible to reduce the amount of water remaining and maintain good physical properties, easy to control the reaction, easy to create various modified polyimide resins, etc. The said isocyanate method (The manufacturing method of the polyimide resin which makes the diisocyanate compound and the compound which has an acid anhydride group react) is preferable.

  Examples of the diamine compound used in the production method 2 include 4,4-diaminodicyclohexylmethane, isophoronediamine, ethylenediamine, tetramethylenediamine, norbornanediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1, Examples include 3-diaminocyclohexane, hexamethylenediamine, polyethylene glycol bis (3-aminopropyl) ether, metaxylylenediamine, 4,4-methylenebis (cyclohexylamine), bicyclohexyldiamine, and siloxane diamine. These diamines can be used alone or in combination of two or more. Among them, diamines having an alicyclic structure such as 4,4-diaminodicyclohexylmethane, isophoronediamine, 1,3-diaminocyclohexane, etc. in terms of easy high molecular weight and excellent heat resistance; Are, for example, oxydianiline, diaminodiphenylmethane, 1,3-phenylenediamine, 1,4-phenylenediamine, dimethylbenzidine, dimethoxybenzidine, diaminodiphenylsulfide, diaminodiphenylsulfoxide, diaminodiphenylsulfone, diaminobenzophenone, 2,2- Bis (3-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3 Hexafluoropropane, 1, -Bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 4 , 4-bis (3-aminophenoxy) biphenyl, 4,4-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl ] Ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- ( 4-aminophenoxy) phenyl] ether, 4,4′-diamino-3,3′-dimethyl-1,1′-biphenyl and the like. It is. These diamines can be used alone or in combination of two or more.

  Examples of the polyisocyanate include aromatic polyisocyanates and aliphatic polyisocyanates.

  Examples of the aromatic polyisocyanate compound include p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4. '-Diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-diethyldiphenyl-4,4'-diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, 1,3-bis (Α, α-dimethylisocyanatomethyl) benzene, tetramethylxylylene diisocyanate, diphenylene ether-4,4′-diisocyanate and naphthalene diisocyanate; the following general formula (a5) Include diisocyanate biphenyl skeleton represented is.

（式中Ｒ_２はそれぞれ独立して水素原子、炭素原子数１〜９のフッ素変性されてもよい炭化水素基を示す。）

(In the formula, each R ₂ independently represents a hydrogen atom or a hydrocarbon group having 1 to 9 carbon atoms which may be fluorine-modified.)

Examples of the diisocyanate represented by the general formula (a5) include 4,4′-diisocyanate-3,3′-dimethyl-1,1′-biphenyl, 4,4′-diisocyanate-3,3′-diethyl. -1,1'-biphenyl, 4,4'-diisocyanate-2,2'-dimethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2'-diethyl-1,1'-biphenyl, Examples include 4,4′-diisocyanate-3,3′-ditrifluoromethyl-1,1′-biphenyl, 4,4′-diisocyanate-2,2′-ditrifluoromethyl-1,1′-biphenyl, and the like.
Etc.

  Examples of the aliphatic polyisocyanate compound include hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylenemethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, and norbornylene diisocyanate.

  As the polyisocyanate compound, it is also possible to use an isocyanate prepolymer obtained by reacting the polyisocyanate compound and various polyol components in advance with an excess of isocyanate groups.

  The polyimide resin used in the present invention may have a branched structure in order to improve solvent solubility and compatibility with other resins. As the branching method, as the polyisocyanate compound, for example, a tri- or higher functional polyisocyanate compound having an isocyanurate ring that is an isocyanurate body such as the diisocyanate compound, a burette body, an adduct body, an allohanate body of the diisocyanate, or Polymethylene polyphenyl polyisocyanate (crude MDI) or the like may be used.

  As the polyisocyanate compound, an aromatic diisocyanate is preferably used since mechanical properties such as mechanical strength and elongation at break and heat resistance of the obtained cured product are improved, and among the aromatic diisocyanates, 4, 4 are preferable. '-Diphenylmethane diisocyanate, tolylene diisocyanate, 4,4'-diisocyanate-3,3'-dimethyl-1,1'-biphenyl is more preferred, and one or more of these diisocyanate compounds, preferably two or more of them are used in combination. Therefore, a cured product having excellent solvent solubility, mechanical properties and heat resistance can be obtained. Furthermore, it is possible to obtain a cured product having further excellent dimensional stability by using one or more, preferably two or more, including 4,4′-diisocyanate-3,3′-dimethyl-1,1′-biphenyl. .

  At this time, when 4,4′-diisocyanate-3,3′-dimethyl-1,1′-biphenyl is used in an amount of 50% by mass or more based on the mass of all polyisocyanate compounds, mechanical properties such as mechanical strength and elongation at break. It is preferable because a cured product having excellent heat resistance can be obtained.

  As a usage-amount of a polyisocyanate compound, 10-70 mol% is preferable on the basis of the molar amount of all the raw materials which comprise a polyimide resin, 10-60 mol% is more preferable, 30-60 mol% is still more preferable.

  Examples of the compound having an acid anhydride group include aromatic tricarboxylic acid anhydrides, alicyclic tricarboxylic acid anhydrides, and tetracarboxylic acid anhydrides. Examples of the aromatic tricarboxylic acid anhydride include trimellitic anhydride and naphthalene-1,2,4-tricarboxylic acid anhydride.

  Examples of the alicyclic tricarboxylic acid anhydride include cyclohexane tricarboxylic acid anhydride. Examples of the cyclohexanetricarboxylic acid anhydride include, for example, cyclohexane-1,3,4-tricarboxylic acid anhydride-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid anhydride-3,5-anhydride, And cyclohexane-1,2,3-tricarboxylic acid anhydride-2,3-anhydride.

  Examples of the tetracarboxylic anhydride include pyromellitic dianhydride, benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride, diphenyl ether-3,3', 4,4'-tetra. Carboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, biphenyl-2,2', 3 , 3'-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4 , 5,8-tetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexa Hydronaphthalene-1,2,5 6-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid bis Anhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,3,9,10-tetracarboxylic dianhydride, berylene-3 , 4,9,10-tetracarboxylic dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 1,1-bis ( 2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride 2,3-bis 3,4-carboxyphenyl) propane dianhydride, bis (3,4-carboxyphenyl) sulfone dianhydride, bis (3,4-carboxyphenyl) ether dianhydride,

Ethylene glycol bisanhydro trimellitate, propylene glycol bis anhydro trimellitate, butanediol bis anhydro trimellitate, hexamethylene glycol bis anhydro trimellitate, polyethylene glycol bis anhydro trimellitate, polypropylene lenglycol bis Anhydro trimellitate, other alkylene glycol bisan hydroxy trimellitate, etc. are mentioned.

  Among the compounds having an acid anhydride group, trimellitic anhydride, cyclohexanetricarboxylic anhydride, pyromellitic dianhydride, benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride, diphenyl ether -3,3 ', 4,4'-tetracarboxylic dianhydride, biphenyl-3,3', 4,4'-tetracarboxylic dianhydride, biphenyl-2,2 ', 3,3'-tetra Carboxylic dianhydrides and ethylene glycol bisanhydro trimellitate are preferred.

  Among the cyclohexanetricarboxylic anhydrides, cyclohexane-1,3,4-tricarboxylic acid anhydrides are obtained because they are excellent in solvent solubility, and a cured product having excellent mechanical properties such as mechanical strength and elongation at break and heat resistance can be obtained. 3,4-anhydride is preferred.

  Here, as the above-mentioned cyclohexanetricarboxylic acid anhydride, a range in which impurities such as cyclohexane-1,2,4-tricarboxylic acid and cyclohexane-1,2,4-tricarboxylic acid used as production raw materials do not impair the curing of the present invention, For example, it may be mixed if it is 10 mass% or less, preferably 5 mass% or less.

  In addition, since a cured product having excellent solvent solubility and a good balance between mechanical properties and heat resistance properties can be obtained, polyimide resin (A) is a polyimide obtained by using cyclohexanetricarboxylic anhydride and trimellitic anhydride in combination. Resin, polyimide resin obtained by using cyclohexanetricarboxylic anhydride and benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride in combination, cyclohexanetricarboxylic anhydride and pyromellitic dianhydride And more preferably a polyimide resin obtained by using a combination of cyclohexanetricarboxylic anhydride, trimellitic anhydride, benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride, pyromellitic acid 2 A polyimide resin obtained by combining two or more selected from the group consisting of anhydrides is more preferred. Further cyclohexane tricarboxylic acid anhydride, trimellitic anhydride, and benzophenone-3,3 ', polyimide resin obtained by a combination of 4,4'-tetracarboxylic dianhydride is more preferred.

  The use amount of the cyclohexanetricarboxylic acid anhydride is 5-100 mol% in the total acid anhydride compound constituting the imide resin becomes a polyimide resin excellent in solvent solubility, and a cured product excellent in mechanical properties and heat resistance. Is preferable, and 10 to 80 mol% is more preferable. The amount of cyclohexanetricarboxylic acid anhydride used is preferably 2 to 60 mol%, more preferably 5 to 50 mol%, based on the molar amount of all raw materials constituting the polyimide resin.

  The amount used when trimellitic anhydride is used in combination with cyclohexanetricarboxylic acid anhydride as the acid anhydride is similarly 5 to 90 mol% cyclohexanetricarboxylic acid anhydride based on the molar amount of the total acid anhydride compound, trimellitic anhydride. The acid is preferably 20 to 90 mol%, more preferably 10 to 50 mol% of cyclohexanetricarboxylic anhydride and 40 to 90 mol% of trimellitic anhydride. Moreover, the usage-amounts of the said cyclohexanetricarboxylic acid anhydride and trimellitic anhydride are 2-60 mol% and 2-60 mol% respectively on the basis of the molar amount of all the raw materials which comprise a polyimide resin.

  When trimellitic anhydride and benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride are used in combination with cyclohexanetricarboxylic acid anhydride as the acid anhydride, the moles of all acid anhydrides constituting the imide resin Preferred is 5 to 90 mol% cyclohexanetricarboxylic anhydride, 2 to 80 mol% trimellitic anhydride, 3 to 50 mol% benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride based on the amount. More preferred are 10 to 80 mol% of cyclohexanetricarboxylic anhydride, 10 to 80 mol% of trimellitic anhydride, and 5 to 30 mol% of benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride. The amount of cyclohexanetricarboxylic anhydride, trimellitic anhydride, and benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride used is based on the molar amount of all raw materials constituting the polyimide resin. Are preferably 2 to 60 mol%, 2 to 60 mol% and 2 to 60 mol%, respectively.

  In the said manufacturing method 1, a polyisocyanate compound and the compound which has an acid anhydride group react. The ratio (ma) / (mb) of the number of moles of isocyanate groups in the polyisocyanate compound (ma) and the total number of moles of non-hydroxyl groups and carboxyl groups in the compound having an acid anhydride group (mb) is expressed as the molecular weight. A ratio of 0.7 to 1.2 is preferable, and a ratio of 0.8 to 1.2 is more preferable because a polyimide resin from which a large polyimide resin can be easily obtained and a cured product having excellent mechanical properties is obtained. Moreover, since it is easy to obtain the polyimide resin which is excellent in storage stability, the (ma) / (mb) is more preferably in the range of 0.9 to 1.1. When other carboxylic acid anhydride is used in combination with cyclohexanetricarboxylic acid anhydride, the above (mb) is the total number of moles of hydroxyl-free and carboxyl groups in all carboxylic acid anhydrides. .

  When the production method 1 is carried out by a one-stage reaction, for example, a reaction vessel is charged with a polyisocyanate compound and a compound having an acid anhydride group, and the reaction proceeds while decarboxylation is performed by raising the temperature while stirring. Let

  The reaction temperature can be in the range of 50 ° C. to 250 ° C., and is preferably performed at a temperature of 70 ° C. to 180 ° C. in terms of reaction rate and prevention of side reactions.

  The reaction is preferable because the stability of the resulting polyimide resin is improved when the reaction is performed until almost all isocyanate groups have reacted. Moreover, you may make it react by adding an alcohol and a phenol compound with respect to the isocyanate group which remains a little.

  In producing the polyimide resin (A) used in the present invention, it is preferable to use an organic solvent because a uniform reaction can proceed. Here, the organic solvent may be present after being present in the system in advance or may be introduced in the middle. In order to maintain an appropriate reaction rate, the proportion of the organic solvent in the system is preferably 98% by mass or less of the reaction system, more preferably 10 to 90% by mass, and more preferably 40 to 90% by mass. % Is more preferable. As such an organic solvent, since a compound containing an isocyanate group is used as a raw material component, an aprotic polar organic solvent having no active proton such as a hydroxyl group or an amino group is preferable.

  As the aprotic polar organic solvent, for example, polar organic solvents such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, and γ-butyrolactone can be used. In addition to the above solvents, ether solvents, ester solvents, ketone solvents, petroleum solvents and the like may be used as long as they are soluble. Various solvents may be mixed and used.

  In particular, the use of γ-butyrolactone is preferred from the viewpoints of the odor and toxicity of the solvent, the reduction of the residual solvent amount upon drying and curing of the coating film, and the reduction of the moisture absorption amount of the solvent of the coating film. Moreover, the structure which melt | dissolves in (gamma) -butyrolactone also in the polyimide resin obtained is preferable. Polyimide resins that are dissolved in such γ-butyrolactone and have good performance in various physical properties (heat resistance, low linear expansion coefficient, mechanical properties) include 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, 4,4′- Using an isocyanate component containing at least one diisocyanate-3,3′-dimethyl-1,1′-biphenyl, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, trimellitic anhydride, It is obtained by reacting The use ratio of the diisocyanate component, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and trimellitic anhydride at this time is based on the molar amount of all raw materials constituting the polyimide resin. 10 to 60 mol%, 2 to 60 mol% and 2 to 60 mol%, respectively, are preferable. Furthermore, it is preferable to use a benzophenone tetracarboxylic acid anhydride as an acid component, so that a cured product having further excellent mechanical properties and the like can be obtained. Similarly, 2 to 20 on the basis of the molar amount of all raw materials constituting the polyimide resin. Mole% is preferred.

  Examples of ether solvents that can be used in the method for producing a polyimide resin used in the present invention include ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Polyethylene glycol dialkyl ethers such as diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, and triethylene glycol dibutyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, etc. Polyethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate Alkyl ether acetates;

Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether; dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol Polypropylene glycol dialkyl ethers such as propylene glycol dibutyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate; Polypropylene glycol monoalkyl ether acetate such as triglycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate Dialkyl ethers of copolymerized polyether glycols such as low molecular weight ethylene-propylene copolymers; monoacetate monoalkyl ethers of copolymerized polyether glycols; alkyl esters of copolymerized polyether glycols; Examples include ether glycol monoalkyl esters and monoalkyl ethers. It is.

  Examples of the ester solvent include ethyl acetate and butyl acetate. Examples of the ketone solvent include acetone, methyl ethyl ketone, and cyclohexanone. In addition, as the petroleum solvent, it is also possible to use toluene, xylene, other high-boiling aromatic solvents, and aliphatic and alicyclic solvents such as hexane and cyclohexane.

  When the synthesis of the polyimide resin (A) used in the present invention is carried out by the amine method, it can be synthesized by using a diamine compound in which the isocyanate group of the isocyanate component used in the above-described isocyanate method is replaced with an amine group.

  Examples of the reaction between the cyclohexanetetracarboxylic dianhydride and the diamine include, for example, adding cyclohexanetetracarboxylic dianhydride to a solution of an organic solvent of diamine, and maintaining the temperature at 4 to 30 ° C. to obtain a polyamic acid solution. Then, the reaction which adds an imidation catalyst and performs dehydration imidation reaction, distilling produced water out of the system is mentioned.

  Examples of the organic solvent in the case of synthesizing an imide resin from the diamine and acid anhydride include the aforementioned organic solvents.

  As an imidization catalyst, tertiary amines such as triethylamine, n-tripropylamine, n-tributylamine, pyridine or β-picoline, or acids such as phenol and benzoic acid can be used. It is preferred to use. The proper molar ratio of these imidation catalyst and diamine (imidation catalyst / diamine) is preferably in the range of 0.01 to 1.0, particularly preferably in the range of 0.05 to 0.1.

  The molar ratio of diamine to cyclohexanetetracarboxylic dianhydride (diamine / cyclohexanetetracarboxylic dianhydride) is preferably in the range of 0.95 to 1.05, particularly in the range of 0.99 to 1.01. Is preferred.

  In the dehydrating imidation reaction in production method 2, the distillate containing water as a main component is removed from the reaction system by a steam cooling tower attached to the upper part of the reaction tank and a distillate storage device engaged therewith. The reaction temperature is usually in the range of 160 to 200 ° C, preferably in the range of 170 to 190 ° C, more preferably in the range of 180 to 190 ° C. If it is lower than 160 ° C., imidation and high molecular weight may not sufficiently proceed due to insufficient temperature, and if it exceeds 200 ° C., a problem such as the resin scorching on the wall of the reaction vessel when the solution viscosity increases remarkably. May occur. In some cases, an azeotropic dehydrating agent such as toluene or xylene may be used. The reaction pressure is usually atmospheric pressure, but the reaction can also be carried out under pressure as necessary. The holding time of the reaction temperature is required to be at least 1 hour, more preferably 3 hours to 10 hours. If it is less than 1 hour, imidization and high molecular weight may not proceed sufficiently. Even if it exceeds 10 hours, the progress of imidization and high molecular weight is not recognized. Moreover, the degree of polymerization of the polyimide resin (A) can be relatively evaluated by measuring the logarithmic viscosity. The logarithmic viscosity is a value measured by dissolving polyimide (A) in N-methyl-2-pyrrolidone at a concentration of 0.5 g / dL at 30 ° C. When the logarithmic viscosity is less than 0.4 dL / g, the degree of polymerization is insufficient and it is difficult to form a self-supporting film, and it is preferably 0.8 dL / g or more.

  The polyimide resin having the structure represented by the general formula (a1-3) may be amidated and imidized by, for example, reacting trimellitic anhydride with 4,4′-diaminodiphenylmethane in the amic acid method. It ’s fine. Moreover, in the said isocyanate method, it can obtain by imidation of a trimellitic anhydride and a methylenebis (phenyl isocyanate). The polyimide resin having the structure represented by the general formula (a1-5) is amidated or imidized by, for example, reacting trimellitic anhydride with an alkyl-substituted biphenyldiamine in the amic acid method. It ’s fine. Moreover, in the said isocyanate method, it can obtain by imidation with trimellitic anhydride and alkyl-substituted biphenyl diisocyanate.

  The polyimide resin having the structure represented by the general formula (a1-4) may be amidated and imidized by, for example, reacting trimellitic anhydride with tolylenediamine in the amic acid method. Moreover, in the said isocyanate method, it can obtain by imidation of a trimellitic anhydride and tolylene diisocyanate.

  The polyimide resin having the structure represented by the general formulas (a2) and (a2-1) is, for example, an imide that undergoes amidation by reaction of cyclohexyltricarboxylic acid anhydride with various diamine compounds in the amic acid method. You just have to. Moreover, in the said isocyanate method, it can obtain similarly by imidation reaction of the anhydride of cyclohexyl tricarboxylic acid and various diisocyanate compounds.

  The polyimide resin having the structure represented by the general formula (a2-2) is obtained by reacting, for example, an anhydride of cyclohexyltricarboxylic acid with 4,4′-diaminodiphenylmethane in the amic acid method, and amidating and imido It's all right. Moreover, in the said isocyanate method, it can obtain by imidation of a trimellitic anhydride and a methylene bisphenyl isocyanate.

  The polyimide resin having the structure represented by the general formula (a2-3) is amidated or imidized by, for example, reacting a cyclohexyltricarboxylic acid anhydride with tolylenediamine in the amic acid method. It ’s fine. Moreover, in the said isocyanate method, it can obtain by imidation of a trimellitic anhydride and tolylene diisocyanate.

  In addition, the polyimide resin having the structure represented by the general formula (a2-4) is obtained by reacting, for example, an anhydride of cyclohexyltricarboxylic acid with an alkyl-substituted biphenyldiamine in the amic acid method, thereby amidating and imido It's all right. Moreover, in the said isocyanate method, it can obtain by imidation with trimellitic anhydride and alkyl-substituted biphenyl diisocyanate.

  The polyimide resin having the structure represented by the general formulas (a4) and (a4-1) is, for example, an imide which undergoes amidation by reaction of benzophenonetetracarboxylic anhydride and various diamine compounds in the amic acid method. You just have to. Moreover, in the said isocyanate method, it can obtain similarly by imidation reaction of a benzophenone tetracarboxylic anhydride and various diisocyanate compounds.

  The polyimide resin having the structure represented by the general formula (a4-2) is, for example, reacted with benzophenone tetracarboxylic anhydride and 4,4′-diaminodiphenylmethane in the amic acid method, and amidated and imidized. Just do it. Further, it can be obtained by imidation of benzophenone tetracarboxylic anhydride and methylene bisphenyl isocyanate in the isocyanate method.

In addition, the polyimide resin having the structure represented by the general formula (a4-3) may be amidated and imidized by, for example, reacting benzophenonetetracarboxylic anhydride and tolylenediamine in the amic acid method. It ’s fine. Moreover, in the said isocyanate method, it can obtain by imidation of a trimellitic anhydride and tolylene diisocyanate.
The polyimide resin having the structure represented by the general formula (a4-4) is obtained by reacting, for example, a benzophenone tetracarboxylic acid anhydride with an alkyl-substituted biphenyldiamine in the amic acid method to obtain an amidation and an imide. It's all right. Moreover, in the said isocyanate method, it can obtain by imidation with trimellitic anhydride and alkyl-substituted biphenyl diisocyanate.

  The polyimide resin (A) used in the present invention has better cyclic solubility by having a cyclic aliphatic hydrocarbon structure such as the structure represented by the general formula (a2-1). Compatibility with the component boron compound (B) and other components is improved, which is preferable. Therefore, having such a structure provides a polyimide-containing thermosetting resin composition that is excellent in storage stability and has good solubility in a solvent even after long-term storage. As the polyimide resin having a cycloaliphatic hydrocarbon structure used in the present invention, among others, a polyimide resin having an imide 5-membered ring structure directly connected to the cycloaliphatic hydrocarbon structure is excellent in storage stability and after long-term storage. It is preferable because it becomes a polyimide resin having good solubility in a solvent and a polyimide resin having excellent mechanical properties such as toughness of the obtained cured coating film.

  As a polyimide resin having an imide 5-membered ring structure directly connected to the cyclic aliphatic hydrocarbon structure, for example, a polyimide resin having the following structure in addition to the structure represented by the general formula (a2-1), etc. It can be illustrated preferably.

In general formula (a5-1) and general formula (a5-2), R ₀ is each independently a divalent diamine or a residue obtained by removing an amine group or an isocyanate group from diisocyanate, and a 0 indicates repetition. , A0 are each 1 to 10,000.

  Examples of the polyimide resin having an imide 5-membered ring structure directly connected to the cycloaliphatic hydrocarbon structure include the general formulas (a1-2), (a2-1), (a4-1), and (a5-1). ) And Ra in the structure of (a5-2) can preferably be exemplified by a polyimide resin having a cyclic aliphatic structure.

  Among the polyimide resins having an imide five-membered ring structure directly connected to the cycloaliphatic hydrocarbon structure, a general formula (a2−) is obtained because a coating film having excellent solvent solubility and excellent mechanical properties such as tensile strength and elongation can be obtained. A polyimide resin having a structure represented by 1) is preferred.

  The content of the general formula (a2-1) in the polyimide resin having the structure represented by the general formula (a2-1) is 1 to 90% by mass based on the solid content mass of the polyimide resin. It is preferable because it is an excellent polyimide resin, and a cured product having excellent mechanical properties such as heat resistance, tensile strength and elongation, and dimensional stability is obtained, and more preferably 2 to 70% by mass. Moreover, 2-50 mass% is more preferable from the crystallinity in the thermosetting resin composition of this invention falling, and the storage stability of the thermosetting resin composition of this invention improves, 3-40 mass % Is more preferable.

  The boron compound (B) used in the present invention is one or more boron compounds selected from the group consisting of the following general formula (b3). By selecting a boron compound having such a structure, it is possible to obtain a cured product having particularly excellent dimensional stability, flame retardancy, thermal decomposition resistance at high temperature, dimensional stability, and mechanical properties. The inventor of the present invention considers that the reason why a cured product having such characteristics is obtained is that an imide moiety or an amide moiety is complexed with a boron moiety.

（式中Ｒ_３はそれぞれ独立して水素原子、炭素原子数１〜４のアルキル基または炭素原子数１〜４のアルコキシ基を表す。Ｚは含窒素複素環化合物を表す。）

(In the formula, each R ₃ independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Z represents a nitrogen-containing heterocyclic compound.)

  Examples of the nitrogen-containing heterocyclic compound include various imidazole compounds represented by pyridine, pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridazine, pyrazine, piperazine, morpholine, pyricidine and the like. It is.

  In the compound represented by (b3), (Z) is preferably an imidazolium salt.

  Examples of the compound represented by (b3) include tetraethyl boron 2-ethyl-4-methyl-imidazole salt as tetraphenyl boron imidazole salt, 2-ethyl-4-methyl-imidazole salt as tetramethyl phenyl boron, and the like. Is mentioned.

  Of the boron compounds represented by the formula (b3), tetraethyl boron 2-ethyl-4-methyl-imidazole salt is more preferable.

  As a composition mixture ratio of the said polyimide resin (A) and a boron compound (B), 0.5-30 mass parts is preferable with respect to 100 mass parts of polyimide resin (A) solid content total. Especially, 0.5-20 mass parts is preferable, and 1-15 mass parts is more preferable.

  In order to prepare the thermosetting resin composition of the present invention, for example, the polyimide resin (A) and the boron compound (B) may be simply mixed or may be dissolved by heating after mixing. As the thermosetting resin composition of the present invention, it is preferable that the boron compound (B) is dissolved. In order to dissolve the boron compound (B), for example, after mixing the polyimide resin (A) and boric acid and / or boron compound (B), 50 to 200 ° C., preferably 80 to 180 ° C. for 1 minute to 60 Stir for minutes.

  In addition to the boron compound (B), a boron compound such as boric acid and / or a boric acid ester can be used in combination with the thermosetting resin composition of the present invention. Examples of such compounds include boric acid; trialkyl such as trimethyl borate, triethyl borate, tributyl borate, tri-n-octyl borate, tri (triethylene glycol methyl ether) borate ester, tricyclohexyl borate, and trimenthyl borate. Linear aliphatic borate esters typified by borate esters; aromatic borate esters such as tri-o-cresyl borate, tri-m-cresyl borate, tri-p-cresyl borate, triphenyl borate, tri Boric acid esters containing two or more boron atoms such as (1,3-butanediol) biborate, tri (2-methyl-2,4-pentanediol) biborate, trioctylene glycol diborate, etc. and containing a cyclic structure ; Polyvinyl alcohol borate ester Xylene glycol anhydrous boric acid to.

  When a compound other than the boron compound (B) is added to the thermosetting resin composition of the present invention, a thermosetting resin composition having good storage stability is obtained, and a cured coating film having excellent dimensional stability is obtained. Therefore, boric acid and linear aliphatic borate esters are preferable. Among the linear aliphatic borate esters, trialkyl borate esters having 4 to 20 carbon atoms are preferable, and tributyl borate (tributyl borate) is particularly preferable.

  Other thermosetting resin components can be further added to the thermosetting resin composition of the present invention. Specifically, an epoxy resin (D), an isocyanate compound, a silicate, an alkoxysilane compound, a melamine resin, etc. are mentioned, for example.

  The epoxy resin preferably has two or more epoxy groups in the molecule. Examples of such epoxy resins include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol S type epoxy resin, and bisphenol F type epoxy resin; novolak types such as phenol novolac epoxy resin, cresol novolac type epoxy resin, and bisphenol type novolak. Epoxy resins; epoxidized products of various dicyclopentadiene-modified phenol resins obtained by reacting dicyclopentadiene with various phenols; biphenyl type epoxy resins such as epoxidized products of 2,2 ', 6,6'-tetramethylbiphenol; Epoxy resin having naphthalene skeleton; aromatic epoxy resin such as epoxy resin having fluorene skeleton and hydrogenated product of these aromatic epoxy resins; neopentyl glycol diglycidyl Aliphatic epoxy resins such as ether and 1,6-hexanediol diglycidyl ether; fats such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and bis- (3,4-epoxycyclohexyl) adipate Cyclic epoxy resins; and heterocyclic ring-containing epoxy resins such as triglycidyl isocyanurate. Among these, an aromatic epoxy resin is preferable because a thermosetting polyimide resin composition excellent in opportunity physical properties of a cured coating film is obtained, and a novolac type epoxy resin is more preferable.

  The blending amount of the polyimide resin (A) and the epoxy resin (D) used in the present invention is such that (A) / (D) is used at a ratio of 1/50 to 50/1 as a mass ratio of the resin. More preferably, it is 1/10 to 10/1.

  Examples of the isocyanate compound include aromatic isocyanate compounds, aliphatic isocyanate compounds, and alicyclic isocyanate compounds. Preferably, a polyisocyanate compound having two or more isocyanate groups in one molecule is preferable. A blocked isocyanate compound can also be used.

  Examples of the alkylalkoxysilane include alkyltrialkoxysilane and dialkyldialkoxysilane.

  Examples of the alkyltrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, Examples thereof include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, and phenyltributoxysilane.

  Examples of the dialkyl dialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, and diphenyldimethoxy. Silane, diphenyldiethoxysilane, diphenyldipropoxysilane, diphenyldibutoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methylethyldipropoxysilane, methylethyldibutoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane , Methylphenyldipropoxysilane, methylphenyldibutoxysilane, trimethylmethoxysilane, trimethyl ether Kishishiran, triethyl silane, triethyl silane, triphenyl methoxy silane, triphenyl ethoxy silane, and the like.

  Moreover, the condensate of alkyl alkoxysilane can also be used, for example, the condensate of the above-mentioned alkyl trialkoxysilane, the condensate of dialkyl dialkoxysilane, etc. are mentioned.

  As the melamine resin, for example, an alkoxylated melamine resin obtained by reacting a part or all of a methylol product obtained by reaction of a triazine ring-containing amino compound such as melamine or benzoguanamine with formaldehyde is used with an alcohol compound. be able to. As the alcohol compound used here, a lower alcohol having about 1 to 4 carbon atoms can be used. Specifically, a methoxymethylolated melamine resin, a butylated methylolated melamine resin, or the like can be used. The molecular structure may be completely alkoxylated, a methylol group may remain, or an imino group may remain.

  This alkoxylated melamine resin, in the thermosetting resin composition of the present invention, has the effect of preventing precipitation with time when boric acid and / or boric acid esters are added in addition to the improvement of heat resistance and physical properties as a crosslinking component. Yes, it improves the stability as a thermosetting resin composition.

  As the resin structure of the alkoxylated melamine resin, the methoxymethylolated melamine resin is preferable because of compatibility with the polyimide resin and good curability at the time of curing, and more preferably, a methoxymethylol having a methoxylation rate of 80% or more. A melamine resin is more preferable.

  The resin structure may be a polynuclear body by self-condensation. The degree of polymerization at this time is preferably about 1 to 5 in terms of compatibility and stability, and more preferably about 1.2 to 3.

  As the number average molecular weight of the alkoxylated melamine resin, those having a molecular weight of 100 to 10,000 can be used. Preferably, 300 to 2000 is preferable in terms of compatibility with the polyimide resin and curability at the time of curing, and more preferably 400 to 1000.

  As the alkoxylated melamine resin, even if melamine, benzoguanamine, formalin and alcohol are simultaneously charged and reacted, melamine or benzoguanamine and formalin are reacted in advance to obtain a methylolated melamine compound and then alkoxylated with the alcohol compound. May be.

  Specific examples of commercially available alkoxylated melamine resins include, for example, product Cymel 300, 301, 303, and 305 manufactured by Nippon Cytec Industries, as methoxymethylolated melamine resins. Examples of the methylol group-containing methoxymethylolated melamine resin include product Cymel 370 and 771 manufactured by Nippon Cytec Industries. Examples of the imino group-containing methoxylated melamine resin include commercial Cymel 325, 327, 701, 703, and 712 manufactured by Mitsui Cytec Co., Ltd. Examples of the methoxylated butoxylated melamine resin include product Cymel 232, 235, 236, 238, 266, 267, 285 manufactured by Nippon Cytec Industries. Examples of the butoxylated melamine resin include product Uban 20SE60 manufactured by Nippon Cytec Industries.

  The amount of the alkoxylated melamine resin used is 1 to 80 parts by mass, preferably 1 to 80 parts by mass with respect to a total of 100 masses of the polyimide resin (A) and boron compound (B) because of excellent mechanical properties and high TG. 50 mass parts and 1-30 mass parts are preferable.

  Further, the thermosetting resin composition of the present invention includes a binder resin such as polyester, phenoxy resin, PPS resin, PPE resin, polyarylene resin, phenol resin, melamine resin, alkoxysilane curing agent, polybasic acid anhydride, cyanate compound. Curing such as curing agents or reactive compounds such as melamine, dicyandiamide, guanamine and derivatives thereof, imidazoles, amines, phenols having one hydroxyl group, organic phosphines, phosphonium salts, quaternary ammonium salts, photocationic catalysts, etc. It is also possible to add a defoaming agent, leveling agent, slip agent, wetting improver, anti-settling agent, flame retardant, antioxidant, ultraviolet absorber, etc. as a catalyst, curing accelerator, further filler, and other additives .

  In addition, various fillers, organic pigments, inorganic pigments, extender pigments, rust inhibitors and the like can be added to the thermosetting resin composition of the present invention as necessary. These may be used alone or in combination of two or more.

  Examples of the filler include barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, and alumina. Is mentioned.

  As the filler, those having various particle sizes can be used, and can be added to such an extent that the physical properties of the present resin and its composition are not impaired. Such an appropriate amount is in the range of about 5 to 80% by mass, and preferably used after being uniformly dispersed. As a dispersion method, it is possible to carry out dispersion by a known roll, bead mill, high-speed dispersion or the like, and the surface of the particles may be modified in advance with a dispersion treatment agent.

  Examples of the organic pigment include azo pigments; copper phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, and quinacridone pigments.

  Examples of the inorganic pigment include chromates such as chrome lead, zinc chromate and molybdate orange; ferrocyanides such as bitumen, titanium oxide, zinc white, bengara, iron oxide; metal oxides such as chromium carbide green, Cadmium yellow, cadmium red; metal sulfides such as mercury sulfide; selenides; sulfates such as lead sulfate; silicates such as ultramarine; carbonates, cobalt biored; phosphates such as manganese purple; aluminum powder, zinc dust Metal powders such as brass powder, magnesium powder, iron powder, copper powder and nickel powder; carbon black and the like.

  In addition, any of other coloring, rust prevention, and extender pigments can be used. These may be used alone or in combination of two or more.

  The thermosetting resin composition of the present invention can be dried or cured by heating at 100 to 300 ° C. after coating or molding.

  The substrate used in the method for forming the coating film can be used without any particular limitation. Examples of the substrate include plastic, metal, wood, glass, inorganic material, and composite materials thereof.

  The thermosetting resin composition of the present invention is a film (adhesive film) comprising a resin and a composition layer (A layer) and a support film (B layer), which is a suitable form for producing a flexible circuit board. ).

  The adhesive film is prepared according to various methods, for example, by preparing a resin varnish obtained by dissolving the thermosetting resin composition of the present invention in an organic solvent, applying the resin varnish to a support film, and heating or blowing hot air. It can manufacture by drying an organic solvent and forming a resin composition layer.

  The support film (B layer) serves as a support when the adhesive film is produced, and is finally peeled off or removed in the production of the flexible circuit board. Examples of the support film include polyolefins such as polyethylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyesters such as polyethylene naphthalate, polycarbonate, and release paper and copper foil. The metal foil etc. can be mentioned. In addition, when using copper foil as a support body film, it can remove by etching with etching liquid, such as ferric chloride and cupric chloride. The support film may be subjected to a release treatment in addition to a mat treatment and a corona treatment, but it is more preferable that the release treatment is performed in consideration of releasability. Although the thickness of a support film is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is used in 25-50 micrometers.

  Organic solvents for preparing the varnish include, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, cellosolve, butyl Examples thereof include carbitols such as carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and gamma butyrolactone. Two or more organic solvents may be used in combination.

  The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition is usually 5% by mass or less, preferably 3% by mass or less. The specific drying conditions vary depending on the curability of the resin composition and the amount of the organic solvent in the varnish. For example, in a varnish containing 30 to 60% by mass of an organic solvent, it is usually 3 to 13 minutes at 80 to 120 ° C. It can be dried to some extent. Those skilled in the art can appropriately set suitable drying conditions by simple experiments.

  The thickness of the resin composition layer (A layer) can usually be in the range of 5 to 500 μm. The preferred range of the thickness of the A layer varies depending on the use of the adhesive film, and when used for manufacturing a multilayer flexible circuit board by the build-up method, the thickness of the conductor layer forming the circuit is usually 5 to 70 μm. The thickness of the A layer corresponding to the layer is preferably in the range of 10 to 100 μm.

  The A layer may be protected with a protective film. By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The protective film is peeled off during lamination. As the protective film, the same material as the support film can be used. Although the thickness of a protective film is not specifically limited, Preferably it is the range of 1-40 micrometers.

  The adhesive film obtained using the thermosetting resin composition of the present invention can be suitably used particularly for the production of multilayer flexible circuit boards. Below, the method to manufacture a multilayer flexible circuit board is demonstrated. The adhesive film obtained using the thermosetting resin composition of the present invention can be suitably laminated on a flexible circuit board by a vacuum laminator. The flexible circuit board used here is mainly composed of a conductive layer (circuit) patterned on one or both sides of a substrate such as a polyester substrate, a polyimide substrate, a polyamideimide substrate, or a liquid crystal polymer substrate, as well as alternating circuits and insulating layers. It is also possible to use a multilayer flexible circuit board that is layered and has a circuit formed on one or both sides for further multilayering. In addition, from the viewpoint of adhesion of the insulating layer to the circuit board, the surface of the circuit should have been previously roughened with a surface treatment agent such as hydrogen peroxide / sulfuric acid or MEC Etch Bond (MEC Co., Ltd.). preferable.

  Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo Morton, a vacuum pressurizing laminator manufactured by Meiki Seisakusho, a roll dry coater manufactured by Hitachi Techno Engineering Co., Ltd., Hitachi AIC ( A vacuum laminator manufactured by Co., Ltd. can be mentioned.

In the lamination, when the adhesive film has a protective film, the protective film is removed, and then the adhesive film is pressure-bonded to the circuit board while being pressurized and heated. The laminating conditions include pre-heating the adhesive film and the circuit board as required, laminating at a pressure of preferably 70 to 140 ° C., a pressure of pressure of preferably 1 to 11 kgf / cm ² and laminating under a reduced pressure of an air pressure of 20 mmHg or less. preferable. The laminating method may be a batch method or a continuous method using a roll.

  After laminating the adhesive film on the circuit board, it is cooled to around room temperature and the support film is peeled off. Next, the thermosetting resin composition laminated on the circuit board is cured by heating. The conditions for heat curing are usually selected in the range of 150 to 220 ° C. for 20 to 180 minutes, more preferably in the range of 160 to 200 ° C. for 30 to 120 minutes. When the support film has a release layer or a release layer such as silicon, the support film can be peeled after the thermosetting resin composition is heat-cured or after heat-curing and punching.

  After the insulating layer, which is a cured product of the thermosetting resin composition, is formed, the via holes and through holes are formed by drilling the circuit board as necessary using a method such as drilling, laser, plasma, or a combination thereof. May be. In particular, drilling with a laser such as a carbon dioxide laser or a YAG laser is generally used.

  Next, surface treatment of the insulating layer (cured product of the thermosetting resin composition) is performed. The surface treatment can employ a method used in a desmear process, and can be performed in a form that also serves as a desmear process. As a chemical used in the desmear process, an oxidizing agent is generally used. Examples of the oxidizing agent include permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, and the like. Preferably, an alkaline permanganate solution (for example, potassium permanganate, sodium hydroxide aqueous solution of sodium permanganate), which is an oxidizer widely used for roughening the insulating layer in the production of multilayer printed wiring boards by the build-up method. It is preferable to carry out the treatment using A treatment with a swelling agent can also be performed before the treatment with the oxidizing agent. Further, after the treatment with an oxidizing agent, neutralization treatment with a reducing agent is usually performed.

  After the surface treatment, a conductor layer is formed by plating on the surface of the insulating layer. The conductor layer can be formed by a method combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. After the conductor layer is formed, the peel strength of the conductor layer can be further improved and stabilized by annealing at 150 to 200 ° C. for 20 to 90 minutes.

  As a method for forming a circuit by patterning the conductor layer, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used. In the case of the subtractive method, the thickness of the electroless copper plating layer is 0.1 to 3 μm, preferably 0.3 to 2 μm. An electroplating layer (panel plating layer) is formed thereon with a thickness of 3 to 35 μm, preferably 5 to 20 μm, an etching resist is formed, and etching is performed with an etching solution such as ferric chloride or cupric chloride. After forming a conductor pattern by this, a circuit board can be obtained by peeling an etching resist. In the case of the semi-additive method, after forming the electroless copper plating layer with an electroless copper plating layer thickness of 0.1 to 3 μm, preferably 0.3 to 2 μm, a pattern resist is formed, and then the electrolytic copper A circuit board can be obtained by peeling after plating.

  A film in which the support film is replaced with a heat-resistant resin layer (heat-resistant resin film), that is, a film comprising the thermosetting composition layer (A layer) and the heat-resistant resin layer (C layer) of the present invention is a flexible circuit board. Can be used as a base film. A film comprising the thermosetting resin composition layer (A layer), the heat-resistant resin layer (C layer) and the copper foil (D layer) of the present invention can be used as a base film of a flexible circuit board as well. In this case, the base film has a layer structure in the order of A layer, C layer, and D layer. In the base film as described above, the heat-resistant resin layer is not peeled off and constitutes a part of the flexible circuit board.

  A film in which an insulating layer (A ′ layer) made of a cured product of the thermosetting resin composition of the present invention is formed on a heat-resistant resin layer (C layer) can be used as a base film for a single-sided flexible circuit board. Moreover, it consists of a film having a layer structure in the order of A ′ layer, C layer and A ′ layer, and A ′ layer, C layer and copper foil (D layer). Similarly, a film having a layer structure can be used as a base film for a double-sided flexible circuit board.

  Examples of the heat-resistant resin used for the heat-resistant resin layer include a polyimide resin, an aramid resin, a polyamideimide resin, and a liquid crystal polymer. In particular, a polyimide resin and a polyamideimide resin are preferable. Moreover, on the characteristic used for a flexible circuit board, the breaking strength is 100 MPa or more, the breaking elongation is 5% or more, the thermal expansion coefficient between 20 and 150 ° C. is 40 ppm or less, and the glass transition temperature is 200 ° C. or more or the decomposition temperature is 300 ° C. It is preferable to use the above heat resistant resin.

  As the heat-resistant resin satisfying such characteristics, a heat-resistant resin that is commercially available in the form of a film can be suitably used. For example, a polyimide film “Upilex-S” manufactured by Ube Industries, Ltd., Toray DuPont Co., Ltd. ) Polyimide film "Kapton", Kaneka Chemical Co., Ltd. polyimide film "Apical", Teijin Advanced Films Ltd. "Aramika", Kuraray Co., Ltd. liquid crystal polymer film "Bexstar", Sumitomo Bakelite Co., Ltd. A polyether ether ketone film “Sumilite FS-1100C” and the like are known.

  The thickness of the heat-resistant resin layer is usually 2 to 150 μm, preferably 10 to 50 μm. As the heat-resistant resin layer (C layer), a surface-treated layer may be used. Examples of the surface treatment include dry treatment such as mat treatment, corona discharge treatment and plasma treatment, chemical treatment such as solvent treatment, acid treatment and alkali treatment, sand blast treatment and mechanical polishing treatment. In particular, from the viewpoint of adhesion to the A layer, it is preferable that plasma treatment is performed.

  A base film for a single-sided flexible circuit board comprising an insulating layer (A ′) and a heat-resistant resin layer (C) can be produced as follows. First, similarly to the adhesive film described above, a resin varnish prepared by dissolving the thermosetting resin composition of the present invention in an organic solvent is prepared, and this resin varnish is applied on a heat-resistant resin film, and heated or blown with hot air or the like. The organic solvent is dried to form a thermosetting resin composition layer. Conditions such as the organic solvent and drying conditions are the same as those for the adhesive film. The thickness of the resin composition layer is preferably in the range of 5 to 15 μm.

  Next, the thermosetting resin composition layer is dried by heating to form an insulating layer of the thermosetting resin composition. The conditions for heat curing are usually selected in the range of 150 to 220 ° C. for 20 to 180 minutes, more preferably in the range of 160 to 200 ° C. for 30 to 120 minutes.

  The production of a base film of a double-sided flexible circuit board film comprising three layers of an insulating layer (A ′ layer), a heat-resistant resin layer (C) layer and a copper foil (D layer) A resin composition may be formed on a copper-clad laminated film made of (D layer) and manufactured in the same manner as described above. Examples of the copper clad laminated film include a cast method two-layer CCL (Copper-clad laminate), a sputtering method two-layer CCL, a laminate method two-layer CCL, and a three-layer CCL. The thickness of the copper foil is preferably 12 μm or 18 μm.

  Commercially available two-layer CCL includes Espanex SC (manufactured by Nippon Steel Chemical Co., Ltd.), Neoprex I <CM>, Neoprex I <LM> (Mitsui Chemicals), S'PERFLEX (Sumitomo Metal Mining Co., Ltd.) Nikaflex F-50VC1 (manufactured by Nikkan Kogyo Co., Ltd.) and the like are mentioned as the commercially available three-layer CCL.

  The production of a base film for a double-sided flexible circuit board film comprising three layers of an insulating layer (A ′ layer), a heat-resistant resin layer (C layer) and an insulating layer (A ′ layer) can be carried out as follows. First, in the same manner as the adhesive film described above, a resin varnish prepared by dissolving the thermosetting resin composition of the present invention in an organic solvent is prepared, and this resin varnish is applied onto a support film, and organic by heating or hot air blowing, etc. The solvent is dried to form a resin composition layer. Conditions such as the organic solvent and drying conditions are the same as those for the adhesive film. The thickness of the resin composition layer is preferably in the range of 5 to 15 μm.

  Next, this adhesive film is laminated on both surfaces of the heat resistant resin film. Lamination conditions are the same as described above. Moreover, if the resin composition layer is previously provided on one side of the heat-resistant film, the lamination may be only on one side. Next, the resin composition layer is cured by heating to form an insulating layer that is a layer of the resin composition. The conditions for heat curing are usually selected in the range of 150 to 220 ° C. for 20 to 180 minutes, more preferably in the range of 160 to 200 ° C. for 30 to 120 minutes.

  A method for producing a flexible circuit board from the base film for the flexible circuit board will be described. In the case of a base film composed of an A ′ layer, a C layer, and an A ′ layer, first, after heat curing, a circuit board is drilled by a method such as drilling, laser, or plasma to form a through hole for conduction on both sides. . In the case of a base film composed of an A ′ layer, a C layer, and a D layer, holes are formed by the same method to form via holes. In particular, drilling with a laser such as a carbon dioxide laser or a YAG laser is generally used.

  Next, a surface treatment of the insulating layer (resin composition layer) is performed. About surface treatment, it is the same as that of the case of the adhesive film mentioned above. After the surface treatment, a conductor layer is formed by plating on the surface of the insulating layer. The formation of the conductor layer by plating is the same as in the case of the adhesive film described above. After the conductor layer is formed, the peel strength of the conductor layer can be further improved and stabilized by annealing at 150 to 200 ° C. for 20 to 90 minutes.

  Next, the conductor layer is patterned to form a circuit to obtain a flexible circuit board. When a base film composed of an A layer, a C layer, and a D layer is used, a circuit is also formed on the copper foil that is the D layer. As a circuit formation method, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used. Details are the same as in the case of the adhesive film described above.

  The single-sided or double-sided flexible circuit board obtained in this way can be produced as a multilayer flexible circuit board by using the adhesive film of the present invention, for example, as described above.

  The resin composition of the present invention is also useful as a material for forming a stress relaxation layer between a semiconductor and a substrate substrate. For example, in the same manner as described above, all or part of the uppermost insulating layer of the substrate substrate is formed by the adhesive film obtained by using the resin composition of the present invention, and the resin is connected by connecting the semiconductor. A semiconductor device in which a semiconductor and a substrate substrate are bonded via a cured product of the composition can be manufactured. In this case, the thickness of the resin composition layer of the adhesive film is appropriately selected within a range of 10 to 1000 μm. The resin composition of the present invention can form a conductor layer by plating, and a circuit pattern can also be produced by simply forming a conductor layer by plating on an insulating layer for stress relaxation provided on a substrate substrate. Is possible.

  Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following, all parts and “%” are based on mass unless otherwise specified.

Synthesis Example 1 [Preparation of polyimide resin (A)]
In a flask equipped with a stirrer, a thermometer and a condenser, 1422.8 g of GBL (gamma-butyrolactone), 250 g (1.0 mol) of MDI (diphenylmethane diisocyanate) and 134.3 (0.7 mol of trimellitic anhydride) were added. ) And 59.4 g (0.3 mol) of TMA-H (cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride), and the temperature was raised to 80 ° C. while stirring while taking care of heat generation. The mixture was heated, dissolved and reacted at this temperature for 1 hour, further heated to 160 ° C. over 2 hours, and then reacted at this temperature for 5 hours. The reaction proceeded with the foaming of carbon dioxide, and the system became a brown transparent liquid. A solution of a polyimide resin (A-1) having a resin solid content of 20% with a viscosity of 10 Pa · s at 25 ° C. and a solution acid value of 1.8 (KOHmg / g) (a resin composition in which the polyimide resin is dissolved in γ-butyrolactone) Product). The acid value of the resin was 1.8 (KOHmg / g). Moreover, it was the weight average molecular weight 64000 as a result of the measurement of a gel permeation chromatography (GPC).

  The obtained polyimide resin (A-1) solution was coated on a KBr plate and the infrared absorption spectrum (FIG. 1) of the sample in which the solvent was volatilized was measured. As a result, 2270 cm-1 which is the characteristic absorption of the isocyanate group was completely obtained. The characteristic absorption of the imide ring was confirmed at 725 cm −1, 1780 cm −1 and 1720 cm −1. The amount of carbon dioxide generated was 88 g (2 mol), which was monitored by the change in the mass charged into the flask. From this, it is concluded that the total amount of 2 moles, which is the total amount of isocyanate groups, has been converted to imide bonds and amide bonds. Furthermore, as a result of analysis by C13-NMR (FIG. 2), it was confirmed that the raw material was a polyimide resin represented by the following structure having a composition ratio of MDI: TMA: TMA-H of 52:35:15 molar ratio. It was done.

However, n: m = 3: 7
In the above structure, the n segment was 0.843 mmol / g, and the m segment was 1.967 mmol / g.

Synthesis example 2 (same as above)
In a flask equipped with a stirrer, a thermometer and a condenser, 1446.3 g of GBL, 240 g (0.96 mol) of MDI, 134.3 (0.7 mol) of TMA and 39.6 g (0.2 mol) of TMA-H And 32.2 g (0.1 mol) of BTDA (benzophenone tetracarboxylic acid anhydride) were added, and the temperature was raised to 170 ° C. over 2 hours with careful attention to heat generation while stirring, followed by reaction at this temperature for 5 hours. I let you. The reaction proceeded with the foaming of carbon dioxide, and the system became a brown transparent liquid. A solution of a polyimide resin (A-2) having a resin solid content of 20% with a viscosity of 8 Pa · s at 25 ° C. and a solution acid value of 2.48 (KOHmg / g) (resin composition in which the polyimide resin is dissolved in γ-butyrolactone) Product). The acid value of the resin was 2.48 (KOHmg / g). Moreover, the weight average molecular weight was 52000 by GPC measurement.

  The obtained polyimide resin (A-2) solution was coated on a KBr plate and the infrared absorption spectrum (FIG. 3) of the sample in which the solvent was volatilized was measured. As a result, 2270 cm-1 which is the characteristic absorption of the isocyanate group was completely obtained. The characteristic absorption of the imide ring was confirmed at 725 cm −1, 1780 cm −1 and 1720 cm −1. The amount of carbon dioxide generated was 84.5 g (1.92 mol), which was tracked by the change in the mass charged into the flask. From this, it is concluded that the total amount of isocyanate groups is converted to imide bonds and amide bonds. Further, as a result of analysis by C13-NMR (FIG. 4), the composition ratio of MDI: TMA: BTDA: TMA-H which is a raw material is a polyimide resin typified by the following structure having a 50: 35: 5: 10 molar ratio. It was confirmed that there was.

但しｎ：ｍ：ｐ＝２：７：１
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However, n: m: p = 2: 7: 1
In the above structure, the n segment was 0.531 mmol / g, the m segment was 1.859 mmol / g, and the p segment was 0.266 mmol / g.

Synthesis example 3 (same as above)
To a flask equipped with a stirrer, a thermometer and a condenser, 1451.2 g of GBL, 125 g (0.5 mol) of MDI and DMBPDI (4,4′-diisocyanate-3,3′-dimethyl-1,1′-biphenyl) 132 g (0.5 mol), TMA 134.4 (0.7 mol) and TMA-H 59.4 g (0.3 mol) were charged, and the mixture was stirred at 160 ° C. over 2 hours while paying attention to heat generation. After raising the temperature to 50 ° C., the reaction was carried out at this temperature for 5 hours. The reaction proceeded with the foaming of carbon dioxide, and the system became a brown transparent liquid. As a result of measuring the viscosity at 25 ° C., the resin solid content was 17% at 6 Pa.s (25 ° C.). This is abbreviated as a solution of polyimide resin (A-3) (resin composition in which polyimide resin is dissolved in γ-butyrolactone). In addition, it is concluded that the average molecular weight is 5960 from the resin solution acid value [3.2 (KOHmg / g)].

  As a result of coating the obtained polyimide resin (A-3) solution on a KBr plate and measuring the infrared absorption spectrum of the sample in which the solvent was volatilized, 2270 cm-1 which is the characteristic absorption of the isocyanate group completely disappeared, Characteristic absorption of the imide ring was confirmed at 725 cm −1, 1780 cm −1 and 1720 cm −1. The amount of carbon dioxide generated was 88 g (2 mol), which was monitored by the change in the mass charged into the flask. From this, it is concluded that the total amount of 2 moles, which is the total amount of isocyanate groups, has been converted to imide bonds and amide bonds.

  Furthermore, as a result of analysis by C13-NMR, it was confirmed that the raw material was a polyimide resin represented by the following structure in which the composition ratio of MDI: DMBPDI: TMA: TMA-H was 25: 25: 35: 15 molar ratio. It was done.

The obtained polyimide resin is a copolymer of the above structures a1 to a4, a1: a2: a3: a4 = 35: 15: 35: 15 molar ratio, and each segment was concluded to have the following molar mass concentration. .
a1: 0.965 mmol / g
a2: 0.413 mmol / g
a3: 0.965 mmol / g
a4: 0.413 mmol / g

Synthesis example 4 (same as above)
A flask equipped with a stirrer, a thermometer and a condenser was charged with 1386.56 g of GBL, 52.2 g (0.3 mol) of TDI (2,4-tolylene diisocyanate) and DMBPDI (4,4′-diisocyanate-3,3). '-Dimethyl-1,1'-biphenyl) 184.8 g (0.7 mol), TMA 138.24 (0.72 mol), and TMA-H 59.4 g (0.3 mol) were charged and stirred. The temperature was raised to 160 ° C. over 2 hours while paying attention to heat generation, and the reaction was carried out at this temperature for 5 hours. The reaction proceeded with the foaming of carbon dioxide, and the system became a brown transparent liquid. As a result of measuring the viscosity at 25 ° C., the resin solid content was 17% at 8 Pa · s (25 ° C.). This is abbreviated as a solution of polyimide resin (A-4) (resin composition in which polyimide resin is dissolved in γ-butyrolactone). From the resin solution acid value [2.9 (KOHmg / g)], it is concluded that the average molecular weight is 6577.

  As a result of coating the obtained polyimide resin (A-4) solution on a KBr plate and measuring the infrared absorption spectrum of the sample in which the solvent was volatilized, 2270 cm-1 which is the characteristic absorption of the isocyanate group completely disappeared, Characteristic absorption of the imide ring was confirmed at 725 cm −1, 1780 cm −1 and 1720 cm −1. The amount of carbon dioxide generated was 88 g (2 mol), which was monitored by the change in the mass charged into the flask. From this, it is concluded that the total amount of 2 moles, which is the total amount of isocyanate groups, has been converted to imide bonds and amide bonds.

  As a result of analysis by C13-NMR, it is a polyimide resin represented by the following structure in which the composition ratio of the raw material TDI: DMBPDI: TMA: TMA-H is 3: 7: 7.2: 3 molar ratio. confirmed.

The obtained polyimide resin is a copolymer of the above structures a1 to a4, a1: a2: a3: a4 = 0.216: 0.09: 0.504: 0.21 molar ratio, and each segment is It was concluded that the following molar mass concentrations:
a1: 0.623 mmol / g
a2: 0.260 mmol / g
a3: 1.453 mmol / g
a4: 0.606 mmol / g

Synthesis example 5 (same as above)
In a flask equipped with a stirrer, thermometer and condenser, 4951 g of EDGA (ethyl diglycol acetate) and a polyisocyanate having an isocyanurate ring derived from isophorone diisocyanate (isocyanate group content: 18.2%, containing isocyanurate ring) Triisocyanate content 85%) 2760 g (12 moles as isocyanate group) and polytail HA [Mitsubishi Chemical Co., Ltd., hydrogenated liquid polybutadiene having hydroxyl groups at both ends, number average molecular weight 2,100, hydroxyl value 51.2 mgKOH / G] 2191 g (2 moles as a hydroxyl group) was charged, and the temperature was raised to 80 ° C. while stirring while paying attention to heat generation. The urethanization reaction was carried out at this temperature for 3 hours. Next, 1536 g of EDGA and 1536 g (8 mol) of EDGA were further added, and the temperature was raised to 160 ° C. and reacted for 4 hours to obtain a light brown polyimide resin (A-5) solution (resin composition in which the polyimide resin was dissolved in EDGA). Obtained. The resin solid content was 48.2%. In addition, it was resin solution acid value [38.1 (KOHmg / g)], and the number average molecular weight was 5,900 and the weight average molecular weight was 24,000 from GPC.

  As a result of coating the obtained polyimide resin (A-5) solution on a KBr plate and measuring the infrared absorption spectrum of the sample in which the solvent was volatilized, 2270 cm-1 which is the characteristic absorption of the isocyanate group completely disappeared, Absorption of the imide ring was confirmed at 725 cm −1, 1780 cm −1 and 1720 cm −1, characteristic absorption of the isocyanurate ring was observed at 1690 cm −1 and 1460 cm −1, and characteristic absorption of the urethane bond was confirmed at 1550 cm −1. The acid value of the polyimide resin was 79 mgKOH / g in terms of solid content, and the concentration of the isocyanurate ring was 0.66 mmol / g (in terms of resin solid content).

Example 1
The thermosetting resin composition 1 of the present invention was prepared with the formulation shown in Table 1. The composition was adjusted by mixing and stirring at room temperature. The obtained thermosetting resin composition 1 was evaluated for solvent solubility, solubility over time, coating workability, heat resistance, flame retardancy, mechanical properties and dimensional stability according to the following methods. The results are shown in Table 3.

(1) Solvent solubility and solubility over time The storage stability test was performed by evaluating the solvent solubility of the thermosetting resin composition 1 immediately after preparation and the solvent solubility after standing for a long period of time. 25 ml of the thermosetting composition immediately after preparation was put into a glass bottle with a lid, the appearance was observed, and the following evaluation criteria were used. This was defined as the solvent solubility of the thermosetting resin composition 1 immediately after preparation. Thereafter, the glass bottle with the lid containing the thermosetting resin composition 1 was allowed to stand at 25 ° C. for 7 days, and then the appearance of the thermosetting resin composition 1 was observed. evaluated.

○: Transparent and fluid.
Δ: Fluidity but turbidity occurs.
×: Applicable to one or more of no transparency, no fluidity, and separation

(2) Evaluation of coating workability The thermosetting resin composition was coated on a tin plate at room temperature with a 0.152 mil applicator. The appearance of the coating was evaluated according to the following evaluation criteria. In addition, when solid content was mixed in the resin solutions prepared in the following Examples and Comparative Examples, the temperature of the resin solution was raised to 120 ° C., and the solid content was once dissolved before coating.

○: Transparent, glossy and flat surface.
Δ: Opaque but flat surface.
X: Opaque and not a flat surface.

(3) Evaluation of heat resistance (1)
The thermosetting resin composition was coated on a glass epoxy substrate laminated with copper so that the film thickness after curing was 30 μm, dried for 60 minutes with a 200 ° C. dryer, cooled to room temperature, and a test piece. It was created. This test piece was immersed in a molten solder bath at 260 ° C. for 30 seconds and cooled to room temperature. This solder bath immersion operation was performed three times in total, and the appearance of the cured coating film was evaluated according to the following evaluation criteria. The heat resistance was also evaluated by measuring Tg described later. The higher the Tg, the better the heat resistance.

○: Appearance abnormality is not observed in the coating film.
Δ: Abnormalities such as swelling and peeling are slightly observed in the coating film.
X: Abnormalities such as swelling and peeling are observed on the entire surface of the coating film.

(4) Heat resistance evaluation (2)
Evaluation was performed by performing pyrolysis measurement.
<Preparation of test piece>
The coating film from which the thermosetting resin composition 1 was obtained was coated on a tin plate so that the film thickness was 30 μm. Next, this coated plate was dried with a dryer at 50 ° C. for 30 minutes, with a dryer at 100 ° C. for 30 minutes, and with a dryer at 200 ° C. for 60 minutes to form a coating film (film). After cooling to room temperature, the coating film (film) was isolated from the substrate and used as a measurement sample.

<Pyrolysis measurement method>
Thermal decomposition was measured by differential thermal-thermogravimetric simultaneous measurement (TG-DGA). Specifically, the thermal weight reduction rate at 500 ° C. was measured with TG / DTA6200 manufactured by SII Nano Technology. For the measurement, the sample was cut into a size that could be enclosed in a measurement aluminum container (70 μl), and the initial sample mass was adjusted between 5.5 and 5.8 mg. Measurement was carried out by heating in a nitrogen stream from room temperature to 500 ° C. at a rate of 10 ° C./min. The evaluation is performed by weight loss%, and the smaller the value, the better the heat resistance.

(5) Evaluation of mechanical properties Mechanical properties were evaluated by conducting a tensile test of a coating film (film) and obtaining elastic modulus, breaking strength and breaking elongation.
<Preparation of test piece>
The coating film from which the thermosetting resin composition was obtained was coated on the tinplate substrate so that the film thickness was 30 μm. Next, this coated plate was dried with a dryer at 50 ° C. for 30 minutes, with a dryer at 100 ° C. for 30 minutes, and with a dryer at 200 ° C. for 60 minutes to form a coating film (film). After cooling to room temperature, the coating film (film) was cut into a predetermined size, isolated from the substrate, and used as a measurement sample.

<Tensile test measurement method>
Five samples for measurement were prepared and subjected to a tensile test under the following conditions to determine the elastic modulus, breaking strength, and breaking elongation. It represents that it is a coating film which is excellent in a softness | flexibility, so that the value of an elasticity modulus is low. It represents that it is a coating film which is excellent in a softness | flexibility, so that the value of breaking elongation is high. And it shows that it is a tough coating film, so that the value of breaking strength is high.
Measuring instrument: Tensilon manufactured by Toyo Baldwin, Inc. Sample shape: 10 mm x 70 mm
Between chucks: 20 mm
Tensile speed: 10 mm / min
Measurement atmosphere: 22 ° C., 45% RH

(6) Evaluation of dimensional stability
<Preparation of test specimen>
The thermosetting resin composition was coated on a tin plate so that the film thickness after curing was 30 μm, dried for 20 minutes with a dryer at 70 ° C., cured for 1 hour at 200 ° C., cooled, and then peeled off. The cured coating film was cut into a width of 5 mm and a length of 30 mm, and used as a measurement sample.

<TG and linear expansion coefficient measurement method>
Using a thermal analysis system TMA-SS6000 manufactured by Seiko Electronics Co., Ltd., measurement was performed by the TMA (Thermal Mechanical Analysis) method under the conditions of a sample length of 10 mm, a heating rate of 10 ° C./min, and a load of 30 mN. In addition, TG calculated | required the inflection point from the temperature-dimension change curve by TMA measurement, and made the temperature TG. Furthermore, the temperature range used for the linear expansion coefficient was determined from the displacement of the sample length at 50 to 60 ° C and 110 to 120 ° C. The smaller the linear expansion coefficient, the better the dimensional stability.

(7) Evaluation of flame retardancy
<Preparation of test specimen>
The thermosetting resin composition was coated on a tin plate so that the film thickness after curing was 30 μm, dried for 20 minutes with a dryer at 70 ° C., cured for 1 hour at 200 ° C., cooled, and then peeled off. The cured coating film was cut into a width of 10 mm and a length of 40 mm, and this film was bent in half in the longitudinal direction to obtain a sample for measurement.

<Flame retardancy evaluation method>
The folded film sample was held horizontally with a clamp, and the flame was slowly ignited with a lighter at the other edge, and the evaluation was performed according to the following criteria.
○: The film sample ignites but disappears immediately.
Δ: The film sample ignites but disappears before the clamp.
X: The film sample burns up to the clamp.

Examples 4, 7, and 10 and Comparative Examples 1 to 5
Thermosetting resin compositions 4, 7, and 10 and comparative thermosetting resin compositions 1 ′ to 5 ′ were prepared in the same manner as in Example 1 except that the compositions shown in Tables 1 to 3 were used. Obtained. Evaluation similar to Example 1 is performed, and the results are shown in Tables 4-6.

  TEPBIZ: 2-ethyl-4-methylimidazolium tetraphenylborate

CNE: Cresol novolac type epoxy resin, epoxy equivalent 214, softening point 80 ° C.
TPP: Triphenylphosphine

Claims (14)

It is a polyimide resin containing a polyimide resin (A) and a boron compound (B) of the following general formula (b3), wherein the polyimide resin (A) has a divalent structural unit represented by the following general formula (a1). The thermosetting resin composition characterized by the above-mentioned.

(In the formula, each R ₃ independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Z represents a nitrogen-containing heterocyclic compound.)

The thermosetting resin composition according to claim 1, wherein Z + of the boron compound represented by the general formula (b3) is an imidazolium salt. The thermosetting resin composition according to claim 1, wherein the content of the boron compound (B) is 0.5 to 30 parts by mass with respect to 100 parts by mass of the polyimide resin. The thermosetting resin composition according to claim 1, wherein the polyimide resin (A) is a polyimide resin having one or more structures represented by the following general formula.

[In the structures represented by the general formulas (a1-3) to (a1-8), * represents a bonding point, and R ₄ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 9 carbon atoms. a1, a2, a3, a4, a5, and a6 are the number of repeating structural units in parentheses and are 1 to 1000, respectively. ] The thermosetting resin composition according to any one of claims 1 to 4, wherein the polyimide resin (A) is a polyimide resin having a cyclic aliphatic hydrocarbon structure. 6. The thermosetting resin composition according to claim 5, wherein the polyimide resin having a cyclic aliphatic hydrocarbon structure is a polyimide resin having an imide 5-membered ring structure directly connected to the cyclic aliphatic hydrocarbon structure. The thermosetting according to claim 6, wherein the polyimide resin having an imide 5-membered ring structure directly connected to the cycloaliphatic hydrocarbon structure is a polyimide resin having a divalent structural unit represented by the following general formula (a2). Resin composition.

The thermosetting resin composition according to claim 7, wherein the polyimide resin having an imide 5-membered ring structure directly connected to the cyclic aliphatic hydrocarbon structure is a polyimide resin having one or more structures represented by the following general formula.

[In the structures represented by the general formulas (a2-3) to (a2-8), * represents a bonding point, and R ₄ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 9 carbon atoms. a7, a8, a9, a10, a11, and a12 are the number of repeating structural units in parentheses and are 1 to 1000, respectively. ] The polyimide resin having the structure represented by the general formula (a2) contains the structure represented by the general formula (a2) at a concentration of 0.02 to 2.0 mmol / g based on the solid content mass of the polyimide resin. The thermosetting resin composition according to claim 7, which is a polyimide resin. Before SL one general formula (A1-7), the general formula (A1-8), according to claim 4 formula (A2-7) and _{R 4} in the structure represented by the general formula (A2-8) is a methyl group Or the thermosetting resin composition of 8. The polyimide resin (A) is a polyimide resin having a structure represented by the following general formula (a1-7) or general formula (a1-8) and general formula (a2-7) or general formula (a2-8). The thermosetting resin composition according to claim 1.
[In the structures represented by the general formulas (a1-7), (a1-8), (a2-7), (a2-8), * is a bonding point, R ₄ is independently a hydrogen atom, carbon Represents a hydrocarbon group having 1 to 9 atoms. a5, a6, a11, and a12 are the number of repeating structural units in parentheses, which are 1 to 1000, respectively. ]

The thermosetting resin according to any one of claims 1 to 11 , wherein a terminal group of the polyimide resin (A) is a carboxylic acid and / or an anhydride of a carboxylic acid, and a solid content acid value is 1 to 50. Composition. The thermosetting resin composition according to claim 12, which is a polyimide resin that is soluble in gamma butyrolactone when the polyimide resin is dissolved in gamma butyrolactone so as to be 10% by mass at 25 ° C. Hardened | cured material formed by hardening | curing the thermosetting resin composition of any one of Claims 1-13.

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